CN117625113A - High-strength bi-component polyurethane pouring sealant and preparation method thereof - Google Patents
High-strength bi-component polyurethane pouring sealant and preparation method thereof Download PDFInfo
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- CN117625113A CN117625113A CN202311696997.4A CN202311696997A CN117625113A CN 117625113 A CN117625113 A CN 117625113A CN 202311696997 A CN202311696997 A CN 202311696997A CN 117625113 A CN117625113 A CN 117625113A
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- 239000000565 sealant Substances 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 30
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims description 82
- -1 urethane polyol Chemical class 0.000 claims description 59
- 150000003077 polyols Chemical class 0.000 claims description 52
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 35
- 229920000570 polyether Polymers 0.000 claims description 35
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 29
- 239000012948 isocyanate Substances 0.000 claims description 24
- 150000002513 isocyanates Chemical class 0.000 claims description 24
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 20
- 239000004359 castor oil Substances 0.000 claims description 19
- 235000019438 castor oil Nutrition 0.000 claims description 19
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 5
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 2
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 5
- 238000004382 potting Methods 0.000 claims 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 125000005498 phthalate group Chemical class 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000010292 electrical insulation Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000306 component Substances 0.000 description 47
- 239000000047 product Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KWUXODGLFDJGBS-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)butoxy]-propylsilane Chemical compound CCC[Si](OC)(OC)OCCC(C)OCC1CO1 KWUXODGLFDJGBS-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Sealing Material Composition (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-strength bi-component polyurethane pouring sealant and a preparation method thereof, belonging to the field of chemical industry. The product provided by the invention is matched by the double components with special compositions, so that the strength and hardness of the product can be controlled, the product is suitable for a fixed scene of a cylindrical battery cell, and meanwhile, the product has good bonding strength, toughness, wet heat resistance, flame retardance, electrical insulation and the like, and the comprehensive performance is excellent.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a high-strength bi-component polyurethane pouring sealant and a preparation method thereof.
Background
In recent years, with the continuous perfection of the industrial chain of new energy vehicles in China, the new energy vehicles are vigorously developed. The power battery is used as a core component of the new energy vehicle, and innovations and developments are advanced. Cylindrical cells have become the main direction of development of power cells due to their high energy density and fast charge characteristics. But compare with square battery cell, it is higher to automobile-used BMS requirement, once the thermal management is effective, the risk of occurence of failure is higher than square battery cell.
At present, the cylindrical battery cells are generally adhered and fixed by using pouring sealant, but the strength of the pouring sealant products still cannot meet the safety requirement of the cylindrical battery cells, and meanwhile, in the application field, the pouring sealant products are required to have enough heat conductivity, flame retardance, wet heat resistance, electrical insulation and hardness.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide the high-strength bi-component polyurethane pouring sealant, and the product is matched by bi-components with special components, so that the strength and hardness of the product can be controlled, the product is suitable for a fixed scene of a cylindrical battery cell, and meanwhile, the product has good toughness, wet heat resistance, flame retardance, electrical insulation and excellent comprehensive performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-strength bi-component polyurethane pouring sealant comprises a component A and a component B;
the component A comprises the following components in parts by weight:
10 to 30 parts of polyol, 40 to 70 parts of aluminum hydroxide, 2 to 5 parts of molecular sieve activated powder, 2 to 10 parts of flame retardant, 0.1 to 0.2 part of defoamer, 1 to 2 parts of coupling agent and 0 to 0.01 part of catalyst;
the polyol is a mixture of polyether polyol and castor oil polyol, and the mass ratio of the polyether polyol to the castor oil polyol is 1: (1-3);
the component B comprises the following components in parts by weight:
20-60 parts of polyurethane prepolymer, 0-20 parts of isocyanate and 20-50 parts of diluent;
the polyurethane prepolymer is obtained by reacting polyether polyol, urethane polyol and isocyanate;
the urethane polyol is obtained by reacting cyclic carbonate with aromatic primary amine, and the melting point of the aromatic primary amine is less than or equal to 100 ℃;
the mass ratio of the component A to the component B is (4-6): 1.
in the components of the high-strength bi-component polyurethane pouring sealant, the polyether polyol and the castor oil polyol in the component A are compounded in the proportion, so that the elongation and the wet heat resistance of a product can be effectively improved, and in the component B, the polyurethane prepolymer is obtained by reacting the urethane polyol with a specific structure with the polyether polyol and isocyanate.
Preferably, the molecular weight of the polyether polyol in the component A is 300-3000, the alcohol hydroxyl value of the castor oil polyol is 160-168 mgKOH/g, and the functionality is 2.5-3.
Under the molecular weight, the two can realize good synergistic effect, and if only polyether polyol or added castor oil polyol is used, the molecular structure of the product contains a large amount of ether bonds, the cohesive energy is low, the mechanical property is weak, but the flexibility is strong; on the contrary, as the content of castor oil increases, the molecular structure of the product contains ester groups and carbon-carbon double bonds, a flexible network with high crosslinking degree is formed, the crosslinking density of the polymer is improved, the mechanical property is enhanced, but the flexibility is reduced, but only castor oil polyol or added polyether polyol is used, the content of the added polyether polyol is too small, and the mechanical property is reduced instead.
It should be noted that "castor oil polyol" in the present embodiment refers to castor oil which contains hydroxyl polyol itself, which is known to those skilled in the art, and is generally obtained by further primary refining of crude castor oil, rather than the product of the castor oil and polyol modification synthesis, which is known to those skilled in the art as "castor oil modified polyol", such as castor oil-based polyether polyol, and is different from the present invention.
More preferably, the mass ratio of the polyether polyol to the castor oil polyol is 1: (1-1.5).
Preferably, the particle diameter D50 of the aluminum hydroxide is 10-20 mu m;
more preferably, the aluminum hydroxide is treated with a silane coupling agent.
After the silane coupling agent is adopted to pretreat the aluminum hydroxide, the compatibility of the inorganic component and other components is obviously improved, high dispersibility can be realized, the effect of strength reinforcement can be achieved, the synergistic flame retardant effect of the flame retardant can be coordinated, and the index of UL 94V 0 can be reached; however, if the size of the aluminum hydroxide is smaller, the viscosity of the pouring sealant is larger, and when the viscosity is too large, the pouring operation of the pouring sealant is not facilitated; the larger the size is, the smaller the specific surface area of the aluminum hydroxide is, so the smaller the probability that the aluminum hydroxide with the same content can be contacted with pouring sealant is, the sparse carbon layer is formed when the pouring sealant is burnt, heat and oxygen invasion are not facilitated to be blocked, the flame-retardant effect is poor, meanwhile, the shearing strength and the tensile strength of a product are also poor, and when the range is preferred, the product can not only consider the good viscosity range and the flame-retardant property, but also consider the good adhesive property and the mechanical property.
Preferably, the molecular sieve activated powder is at least one of 3A molecular sieve activated powder, 4A molecular sieve activated powder and 5A molecular sieve activated powder.
More preferably, the weight part of the molecular sieve activating powder in the component A is 1-3 parts.
Preferably, the flame retardant is at least one of ammonium polyphosphate and phosphate.
More preferably, the flame retardant is a microcapsule particle or a core-shell structured particle.
Preferably, the defoamer is an organomodified polysiloxane.
Preferably, the coupling agent is at least one of gamma-glycidoxypropyl trimethoxysilane, gamma- (2, 3 glycidoxypropyl) propyl trimethoxysilane, ureidopropyl triethoxysilane, beta- (3, 4 epoxycyclohexyl) -ethyl trimethoxysilane, gamma-ureidopropyl trimethoxysilane.
Preferably, the catalyst is at least one of organobismuth, organozinc and dibutyltin dilaurate.
More preferably, the catalyst is a complex of organobismuth and organozinc.
Preferably, the isocyanate is at least one of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate.
Preferably, the diluent is at least one of phthalate esters and aliphatic diacids.
Preferably, the cyclic carbonate is at least one of propylene carbonate and ethylene carbonate, and the aromatic primary amine is at least one of m-xylylenediamine (melting point 14 ℃), 4 '-methylenebis (2-ethylaniline) (melting point 46 ℃), m-phenylenediamine (melting point 64-66 ℃), 4' -diaminodiphenylmethane (melting point 89-91 ℃), and 1,3, 5-triaminobenzene (melting point 84-85 ℃).
The low-melting aromatic primary amine has lower temperature than the liquid state melting at a high melting point, and the liquid state is convenient for full reaction with the cyclic carbonate; the high-melting-point aromatic primary amine is melted into the liquid state at a higher temperature, and is more violent when being dripped into the cyclic carbonate for reaction, the reaction is not easy to control, and the reaction product is impure due to extremely easy oxidation.
More preferably, the molar ratio of cyclic carbonate to aromatic primary amine is f:1, wherein f is the functionality of an aromatic primary amine.
More preferably, the urethane polyol is obtained by reacting a cyclic carbonate with an aromatic primary amine at 60 to 90 ℃ for 3 to 6 hours.
More preferably, the urethane polyol is prepared by the following steps: and (3) placing the cyclic carbonate with the proportioning amount into a reaction vessel, heating to the reaction temperature, dropwise adding the aromatic primary amine with the proportioning amount under the protection of nitrogen, and reacting to obtain the urethane polyol.
Preferably, in the preparation raw materials of the polyurethane prepolymer, the mass ratio of the polyether polyol to the urethane polyol is 5: (1 to 3), more preferably 5: (1.5-2.5).
The preferable result shows that when the addition amount of the urethane polyol is smaller, the strength of the polyurethane pouring sealant is improved less; when the addition amount is too high, the viscosity of the polyurethane prepolymer can be greatly improved, so that the pouring sealant is not easy to construct and operate.
More preferably, the preparation method of the polyurethane prepolymer comprises the following steps: mixing the polyether polyol and the urethane polyol in a proportion, vacuum drying for 2-3 h at 100-120 ℃, then cooling to below 40 ℃, adding isocyanate under the protection of nitrogen, and heating to 50-60 ℃ for reacting for 2-3 h to obtain the polyurethane prepolymer.
More preferably, the NCO content of the polyurethane prepolymer is 10 to 25%, more preferably 16 to 23%.
The invention further aims at providing a preparation method of the high-strength bi-component polyurethane pouring sealant, which comprises the following steps:
mixing and heating the polyol, the aluminum hydroxide and the flame retardant to 110-130 ℃, then vacuum drying for 2-4 hours, cooling to 40-60 ℃, then adding other components and uniformly mixing in a vacuum state to obtain a component A;
and (3) pre-drying and dehydrating the diluent, and then uniformly mixing the diluent with polyurethane prepolymer and isocyanate in a vacuum state to obtain the component B.
The preparation method of the high-strength bi-component polyurethane pouring sealant has simple operation steps and low requirements on production conditions and setting, and can realize industrial production.
The invention has the beneficial effects that the high-strength bi-component polyurethane pouring sealant provided by the invention is matched by the bi-components with special components, so that the strength and hardness of the product can be controlled, the product is suitable for a fixed scene of a cylindrical battery cell, and meanwhile, the product has good toughness, wet heat resistance, flame retardance, electrical insulation and excellent comprehensive performance.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
Examples 1 to 12
The embodiment of the high-strength polyurethane pouring sealant and the preparation method thereof provided by the invention comprises the following steps:
mixing and heating the polyol, the aluminum hydroxide and the flame retardant to 120 ℃, then vacuum drying for 3 hours, cooling to 50 ℃, then adding other components and uniformly mixing in a vacuum state to obtain a component A;
and (3) pre-drying and dehydrating the diluent, and then uniformly mixing the diluent with polyurethane prepolymer and isocyanate in a vacuum state to obtain the component B.
The composition ratio of the component A and the component B is shown in the table 1.
In the component A, polyether polyol 1 is polyether glycol and has a molecular weight of 1000; the polyether polyol 2 is polyether glycol with a molecular weight of 2000; the castor oil polyol is first-grade castor oil produced by Fucheng county oil Limited company, the hydroxyl value of alcohol is 163mgKOH/g, and the functionality is 2.7.
In the component A, aluminum hydroxide 1 is aluminum hydroxide with the particle diameter D50=10μm activated by a silane coupling agent; aluminum hydroxide 2 is aluminum hydroxide with a particle diameter d50=20 μm activated by a silane coupling agent; aluminum hydroxide 3 is aluminum hydroxide with a particle diameter d50=5 μm activated by a silane coupling agent; aluminum hydroxide 4 is aluminum hydroxide having a particle diameter d50=50 μm activated by a silane coupling agent.
The molecular sieve activating powder in the component A is 3A molecular sieve activating powder, and 3A molecular sieve activating powder is produced by Jiangxi Xin Tao technology Co., ltd.
The flame retardant in the component A is microcapsule ammonium polyphosphate, and melamine coated modified ammonium polyphosphate flame retardant is produced by Shenzhen City neutralization science and technology Co.
The catalyst in the component A is a commercially available organic bismuth-zinc catalyst compound.
The defoaming agent in the component A is organic modified polysiloxane, and LeAd 220 defoaming agent is produced by Guangzhou Wen Ba chemical company.
The coupling agent in the component A is gamma-glycidyl ether oxypropyl trimethoxy silane.
In the component B, the polyurethane prepolymer 1-3 is prepared by reacting polyether polyol, urethane polyol and isocyanate, and the preparation method comprises the following steps: polyether polyol and urethane polyol are mixed according to a ratio of 5:2 (total 100 g), vacuum dried for 3 hours at 120 ℃, then cooled to below 40 ℃, blocked by adding isocyanate (410 g of isocyanate is added to polyurethane prepolymer 1, 410g of isocyanate is added to polyurethane prepolymer 2, 190g of isocyanate is added to polyurethane prepolymer 3) under the protection of nitrogen, and heated to 60 ℃ for reaction for 3 hours, so that the polyurethane prepolymer is obtained, and the NCO content is 16-23%.
Wherein polyether polyol a is polyether triol, the molecular weight is 3000, the functionality is 3, polyether polyol b is polyether diol, the molecular weight is 2000, and the functionality is 2; the isocyanate is a mixture of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate;
the urethane polyol 1-2 is obtained by reacting cyclic carbonate with aromatic primary amine. The preparation method comprises the following steps: and (3) placing the cyclic carbonate with the proportioning amount in a reaction vessel, then heating to 80 ℃, dropwise adding the aromatic primary amine with the proportioning amount under the protection of nitrogen, and reacting for 5 hours to obtain the urethane polyol.
Wherein the molar ratio of cyclic carbonate to aromatic primary amine is f:1, wherein f is the functionality of an aromatic primary amine, wherein a urethane polyol 1 is obtained by reacting a cyclic carbonate 1 with the aromatic primary amine 1, and a urethane polyol 2 is obtained by reacting a cyclic carbonate 2 with the aromatic primary amine 2; the cyclic carbonate 1 is propylene carbonate, the cyclic carbonate 2 is ethylene carbonate, the aromatic primary amine 1 is m-xylylenediamine, and the aromatic primary amine 2 is 4,4' -diaminodiphenylmethane.
The details are shown in the following table.
Comparative examples 1 to 3
A polyurethane pouring sealant and a preparation method thereof, which only differ from example 1 in the amount of each component, as shown in table 2.
Comparative example 4
The polyurethane pouring sealant and the preparation method thereof only differ from the embodiment 1 in that the polyurethane prepolymer 5 is obtained by reacting polyether polyol, polyethylene glycol (molecular weight 400 g/mol) and isocyanate, and the preparation method comprises the following steps: mixing polyether polyol and urethane polyol according to a ratio of 5:2, vacuum drying at 120 ℃ for 3 hours, cooling to below 40 ℃, adding isocyanate under the protection of nitrogen, and heating to 60 ℃ for reaction for 3 hours to obtain the polyurethane prepolymer 4.
Comparative example 5
The polyurethane pouring sealant and the preparation method thereof only differ from the embodiment 1 in that the polyurethane prepolymer 6 is obtained by reacting polyether polyol, urethane polyol and isocyanate, and the preparation method comprises the following steps: mixing polyether polyol and urethane polyol according to a ratio of 5:2, vacuum drying at 120 ℃ for 3 hours, then cooling to below 40 ℃, adding isocyanate under the protection of nitrogen, and heating to 60 ℃ for reaction for 3 hours to obtain the polyurethane prepolymer 5;
the urethane polyol is obtained by reacting cyclic carbonate with aliphatic primary amine propylene diamine. The preparation method comprises the following steps: the cyclic carbonate 1 with the proportioning amount is placed in a reaction vessel, then heated to 80 ℃, and the aromatic primary amine with the proportioning amount is added dropwise for reaction for 5 hours, so as to obtain the urethane polyol.
Comparative example 6
The polyurethane pouring sealant and the preparation method thereof only differ from the embodiment 1 in that the polyurethane prepolymer 7 is obtained by reacting polyether polyol, urethane polyol and isocyanate, and the preparation method comprises the following steps: mixing polyether polyol and urethane polyol according to a ratio of 5:2, vacuum drying at 120 ℃ for 3 hours, then cooling to below 40 ℃, adding isocyanate under the protection of nitrogen, and heating to 60 ℃ for reaction for 3 hours to obtain the polyurethane prepolymer 6;
the urethane polyol is obtained by reacting cyclic carbonate with aliphatic primary amine ethylenediamine. The preparation method comprises the following steps: the cyclic carbonate 1 with the proportion is placed in a reaction vessel, then heated to 80 ℃, ethylenediamine with the proportion is added dropwise and reacted for 5 hours, and the urethane polyol is obtained.
TABLE 1
TABLE 2
Effect example 1
In order to verify the use performance of the high-strength two-component polyurethane pouring sealant of the present invention, the following test was performed on each of examples and comparative examples and on the commercial polyurethane pouring sealant of the Bonac new technology Co., ltd:
TABLE 3 Table 3
As can be seen from the table, the viscosity of the high-strength bi-component polyurethane pouring sealant prepared by the invention can be maintained within the range of 3500-7000+/-500 cps, construction is not influenced by too high or too low viscosity, meanwhile, the hardness is far higher than that of a commercial product, the shearing strength on an aluminum substrate can reach 12.5MPa or more, the tensile strength can reach 13.5MPa or more, the flame retardance can reach UL 94V 0, the comprehensive performance is excellent, and the high-strength bi-component polyurethane pouring sealant can completely replace the existing commercial product. In contrast, the product of comparative example 1 had excessive addition of polyurethane prepolymer during compounding, resulting in excessive viscosity of the product, and failure to perform construction, and also had reduced flame retardant properties as compared with the product of example 1. The compounding ratio of the polyalcohol in comparative examples 2 and 3 is improper, and the shearing strength and the tensile strength of the product are greatly reduced; comparative examples 4 to 6 were unsuitable in the kind of raw materials used in the preparation of polyurethane prepolymer, and the prepared products could not achieve the comprehensive properties of the example products.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The high-strength bi-component polyurethane pouring sealant is characterized by comprising a component A and a component B;
the component A comprises the following components in parts by weight:
10 to 30 parts of polyol, 40 to 70 parts of aluminum hydroxide, 2 to 5 parts of molecular sieve activated powder, 2 to 10 parts of flame retardant, 0.1 to 0.2 part of defoamer, 1 to 2 parts of coupling agent and 0 to 0.01 part of catalyst;
the polyol is a mixture of polyether polyol and castor oil polyol, and the mass ratio of the polyether polyol to the castor oil polyol is 1:
(1～3)；
the component B comprises the following components in parts by weight:
20-60 parts of polyurethane prepolymer, 0-20 parts of isocyanate and 20-50 parts of diluent;
the polyurethane prepolymer is obtained by reacting polyether polyol, urethane polyol and isocyanate;
the urethane polyol is obtained by reacting cyclic carbonate with aromatic primary amine, and the melting point of the aromatic primary amine is less than or equal to 100 ℃;
the mass ratio of the component A to the component B is (4-6): 1.
2. the high strength two-component polyurethane potting adhesive of claim 1, wherein the polyether polyol in the A component has a molecular weight of 300-3000, the castor oil polyol has an alcohol hydroxyl value of 160-168 mgKOH/g, and a functionality of 2.5-3.
3. The high strength two-component polyurethane potting adhesive of claim 1, wherein the particle size D50 of the aluminum hydroxide is 5 to 20 μm.
4. The high strength two-component polyurethane potting adhesive of claim 1, comprising at least one of the following (a) to (f):
(a) The molecular sieve activated powder is at least one of 3A molecular sieve activated powder, 4A molecular sieve activated powder and 5A molecular sieve activated powder;
(b) The flame retardant is at least one of ammonium polyphosphate and phosphate;
(c) The defoaming agent is organic modified polysiloxane;
(e) The coupling agent is at least one of gamma-glycidol ether oxypropyl trimethoxy silane, gamma- (2, 3 epoxy propoxy) propyl trimethoxy silane, ureido propyl triethoxy silane, beta- (3, 4 epoxy cyclohexyl) -ethyl trimethoxy silane and gamma-ureido propyl trimethoxy silane;
(f) The catalyst is at least one of organic bismuth, organic zinc and dibutyl tin dilaurate.
5. The high strength two-component polyurethane potting adhesive of claim 1, wherein the isocyanate is at least one of diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate.
6. The high strength two-component polyurethane potting adhesive of claim 1, wherein the diluent is at least one of phthalates and aliphatic diacids.
7. The high-strength two-component polyurethane pouring sealant according to claim 1, wherein the cyclic carbonate is at least one of propylene carbonate and ethylene carbonate, and the aromatic primary amine is at least one of m-xylylenediamine, 4 '-methylenebis (2-ethylaniline), m-phenylenediamine, 4' -diaminodiphenylmethane, and 1,3, 5-triaminobenzene.
8. The high-strength two-component polyurethane pouring sealant according to claim 1, wherein the urethane polyol is obtained by reacting a cyclic carbonate with an aromatic primary amine at 60-90 ℃ for 3-6 hours.
9. The high-strength two-component polyurethane pouring sealant according to claim 1, wherein the mass ratio of polyether polyol to urethane polyol in the preparation raw material of the polyurethane prepolymer is 5: (1-3); preferably, the preparation method of the polyurethane prepolymer comprises the following steps: mixing the polyether polyol and the urethane polyol in a proportion, vacuum drying for 2-3 h at 100-120 ℃, then cooling to below 40 ℃, adding isocyanate under the protection of nitrogen, and heating to 50-60 ℃ for reacting for 2-3 h to obtain the polyurethane prepolymer.
10. The method for preparing the high-strength two-component polyurethane pouring sealant according to any one of claims 1 to 9, which is characterized by comprising the following steps:
mixing and heating the polyol, the aluminum hydroxide and the flame retardant to 110-130 ℃, then vacuum drying for 2-4 hours, cooling to 40-60 ℃, then adding other components and uniformly mixing in a vacuum state to obtain a component A;
and (3) pre-drying and dehydrating the diluent, and then uniformly mixing the diluent with polyurethane prepolymer and isocyanate in a vacuum state to obtain the component B.
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